CA2180852A1 - Anthraquinone dyes containing a fluorosulphonyl group and use thereof - Google Patents
Anthraquinone dyes containing a fluorosulphonyl group and use thereofInfo
- Publication number
- CA2180852A1 CA2180852A1 CA002180852A CA2180852A CA2180852A1 CA 2180852 A1 CA2180852 A1 CA 2180852A1 CA 002180852 A CA002180852 A CA 002180852A CA 2180852 A CA2180852 A CA 2180852A CA 2180852 A1 CA2180852 A1 CA 2180852A1
- Authority
- CA
- Canada
- Prior art keywords
- amino
- dioxo
- dihydro
- ring
- so2f
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/78—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring with other reactive groups
- C09B62/80—Anthracene dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/16—Amino-anthraquinones
- C09B1/20—Preparation from starting materials already containing the anthracene nucleus
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/56—Mercapto-anthraquinones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/26—Polyamides; Polyurethanes using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/34—Material containing ester groups
- D06P3/52—Polyesters
- D06P3/54—Polyesters using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/70—Material containing nitrile groups
- D06P3/72—Material containing nitrile groups using dispersed dyestuffs
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/79—Polyolefins
- D06P3/794—Polyolefins using dispersed dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/82—Textiles which contain different kinds of fibres
- D06P3/8204—Textiles which contain different kinds of fibres fibres of different chemical nature
- D06P3/8223—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups
- D06P3/8228—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye
- D06P3/8233—Textiles which contain different kinds of fibres fibres of different chemical nature mixtures of fibres containing hydroxyl and ester groups using one kind of dye using dispersed dyes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/922—Polyester fiber
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
A process for colouring a synthetic textile material or fibre blend thereof which comprises applying to the synthetic textile material a compound of formula (1) wherein Ring A and Ring D are optionally substituted and at least one of Ring A or Ring D carries at least one -SO2F group except for 2-¢(9,10-dihydro-9,10-dioxo-1-anthracenyl)amino!-ethanesulphonylfluoride, 2-¢(9,10-dihydro-9,10-dioxo-2-anthracenyl)amino!-ethanesulphonylfluoride, 2,2'-¢(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino!bisethanesulphonylfluoride, 2,2'¢(9,10-dihydro-9,10-dioxo-1,5-anthracenediyl)diimino!bisethanesulphonylfluoride, 2,2'-¢(9,10-dihydro-2-methoxy-9,10-dioxo-1,4-anthracenediyl)diimino! bisethanesulphonylfluoride, 2¢(4-(benzoylamino)-9,10-dihydro-9,10-dioxo-1-anthracenyl)amino! ethanesulphonylfluoride, 2-¢(9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl)amino!ethane sulphonylfluoride.
Description
Anthri~qu1ncne dyes conta1n~ng a fluorcsulphonyl groUp and use th~reof The present invention relates to a process _or colourin~
sy~thetic textile materials, to ~ynt_etic textiles when colc~red, to a process for the mass rnlnr~t;nn of plastics, to plastics when coloured to certa~r novel ~ dyes and to, tinnc . ~ .J
~ dyes.
ccording to t_e 7~resent invention there is provided a process for colouring a synthetic textile material or f~ore Jlend t_ereof which cc~prises applying to the synthetic textile material a compld of Fora~la ( 1 ~:
Forrnula (1 wherein Ring A and Ring D æe nrt~nn~lly ~lh~st~tlltp~ and at least one of ~ily A
or Ring D carries at least one -SO,F group except for 2- [(9,l0-d;hydro-g,3:0-dioxo-l--.,1 l,._, ~yl)amino] -oth~n~clllrhnny~fllln 2-t(9,10-d;hydro-9,10-dloxo-2-~ y~ no]-~th:~noclllrhnnylfllmr;~
2,2'-[(9,10-dihydro-9,10-dioxo-1,4-~.,11"~ ,l;yl)diimino]h;c~h~n Sulp7~onyl flllnr;~O, 25 2,2'-[(9,10-dihycro-9,10-dioxo-1,5-,.. 1l.. _. .. ~.l;yl)diimino]h;c~th~no sul ~honylfluoride, 2,2'- [(9,10-dihydro-2-methoxy-9,10-dioxo-1,4-r...l 1~ ;yl)diimino) h;coth~noclllrhnnylflllnr;~9~
2 - [ (4- (~z;oylamino) - 9, 10-dihydro- 9 ,10-dioxo-l-- .I l,, _. -. yl] amino]~th~noclllrhnnylfllmr;~o 2- [ (9,10-dihydro-4- (met~ylamino) -9, 10-dioxo-l-_. .1 7" ,.. -"yl] amino] eth ne s~lphonyl fl llnr; ~O
7~;ffc-ront, ' of For~ la (l) mi~y ~e mixed or the cc~o~ s of Formllla (1) may ~e mixed with dyes which do not contain ~n -SO,F group, suc~ mixtures æe a feature of the prese~t invention.
The mixtures l;ay 70e simple physical mixtures or mi~y ~e mixed cryst~l s ~ormod ~or exallple ~y co-cry~ tAl l i q~t~ nn Such mixtures gener lly show , v~ in dyeing properties. Crystallirle ~;;~;r~t,nnc 0_ compaun~s of Formula (1~ exist and it is intended that the present 'o~;n~t;nn illcl7~des such crystalline ~;f;r~t~nn~ whic7l may ~or e~3mple ~e fo~med hy heat tro~trlont, SUaSTlTUTE SHEET (RULE 26) _ _ WO 95/21958 ~ 5 - /
2~ 52 2 n-T to a ~urther ~eatT~re o~ the presQ-nt ~ven~ion there is pmYided a pmcefis for colouring a polyester textile Trateri 1 or fibre blend t_ereof which comprises applYiTlg to t_e polyester textile material 2-t(9,10-dihYdm-9,10-dioxo-1~ T,...~ yl)aTr~no]-Pth~nPQllirhnnylf7llnr~rlp~
2-[(9,10-dihYdm-9,10-dioxo-2-,."~ ,,yl)a~ no]-pthAnc~Qlllrhnnylflllnr~
2,2'-[(9,lO-dihYdm-9,10-dioxo-1,4-~ l;yl)oiimi~o3--isethAne alllrhnnylf~llnr~P, 2,2'-[(9,10-dihYdm-9,10-dioxo-1,5-,."11 .,. - ~l;yl)diimino~biseth ne 51.1ph0nYl flllnr~P, 2,2'-[~9,lO-dihYdm-:2-methoxy-9,10-dioxo-1,4-A.. ll,.A.. ~ ;yl)dii) h~ QPth:lnpclllrhnnyl flllnr~lP, 2- ~ (4- (benzoYlaTrino) ~9,10-dihY~m-9,10-dioxc-1-,. ,l 1".,.,, yl]aTr~no]
PthAnPClllrhnnyl flllnr~-lo, 2- [ (9,10-dihYdm-4- (meth--ylaTrino) -9, 10-dioxo-1-~ yl] aTr~no~ eth~rP
sulph~nYl f l 1 1nr~ rlP .
The Fresence of one or Trore -SO.F gmups in a dye molecule generally impmYes t~le Fr~7Prt~Pc of tùat dye a~d confers cll~r~c~n~ly good wet-fastness a~d light-fastness rmrPrti~a.
The synthetic textile material Tray be selected fmm secondarY
cellulose acetate, cellulose tr~ArPtAtP~ Folyamide, polyacrYlonitrile ~d arT~rratic polyester. The synt_etic textile material is Fre-ferah-ly FlYamide or amTratic polYester, such as pol,' ', lene adiFamide or Folyethylene tPrPrht~lAlAtp more preferably =tic Folyester and especially poly-ethlene tPrPrhthAlRtP~ Pibre blPn~Q my comprise mixtures of ~;ffPrPnt synthetlc textile materials or m~CtureS of synthetic and nat~r-Al textile --~Pri~lc. Preferred fibre bLendfi are those of Folyester-cellulose sUch- as Folyester-cotton. The textile materials or hler~ds t_ereof may be in the ~orm of filaments, loose fibres, yarn, woYen or knitted fis.
The dYes of For~la (1) FrefPr~hly haYe low solT~bility in water, tYpiC lly less th~n 1~6 preferabLy lesg them 0.59~ alld esperiAlly less than 0.296 Qnlllhil;ty in water. The dyes of For~la (1) are t~h-us free fmm water snlllhil;Qin~ Qs such as -SO,II, -CO2i/, -PO,Il and LL~:L I IA ' y amino .
The dres of Formula (1), optionally in conjunction with other disperfie dyes Tray be applied to the sy~thetic textile materials or fibre blPn~C thereof by Trethods which are conYentionally employed in dyeing disFerse dyes to such mAtPriAlC a~d fibre blentis. For e~mple, the dyes of FormuLa (1) in the form of an aqueous rl;crPrQ~nn may be a~?pliel by dyeiny, padding or printing ~L~ a~e:S ufiing the rnn~;t;nnc and additiYes conY~ntirnAlly used in carrying out such pmcesses.
The pmcess rnnrlitirnQ Tray be selected fmm t_e following:
i) exhaust dyei~y at a plI of fr~m 4 to 6.5, at a L _ of fr~n 125C to 140C for fmm 10 to 120 minutes and u~der a pressure of fmm 1 to 2 bar, a ~ All may be opti~ally be added SUBSTITUTE SHEET (RULE 26~
WO 95~1958 2 1 8 0 8 5 2 dyeing at a pEl of ~rom 4 to 6.5, at a; , of from 190C to 225C for from 15 secon~s to 5 m~utes, a migration inhiitor may option lly be added;
iii~ printing direct at a r~ of from 4 to 6.5, at a i , of from 5 160C to 185C for 4 to 15 minutes for high L , ' steami~g, or at a t, of from 190C to 225C for 15 seoon~s to 5 minutes for Ake fixation with d~y h-eat or at a t , of from 120C to 140C a~d 1 to 2 bar for 10 to 45 m~nutes for pressure steam~Ilg, wetting agents a~l th;rl-PnPrc (such as ~lginates~ of from 5 to 100S by weight of the dye may be optionally be ad~ed;
iv~ ~t~$rh~e rri~ting (hy paddirlg the dye onto t_e textile material, dry~ng nd uv~ ) at a pE of from 4 to 6.5, migration ,nh;h-tnrc al~d thlrlopn~rc may option lly he added;
v~ carrier dyei~ at a pH of from 4 to 6.5, at a L , ' of from 95C to 100C usillg a carrier suc_ as met_yln~rhth;llPnP, diphPnylamine or 2-r~enylphenol, ~r~ may optionally ~e added; and Vi~ ;r dyeiIy of acetate, trlArPt~tP and nylon at a pE~ of from 4 to 6.5, at a t, ' of 85C for acetate or at a;
of 90C for tro~rPt~tP and nylon for frc~m 15 to 90 miI~utes, ~r ~ may opt rn~lly he added.
In all t_e a~ove ~u~____ the compound of ForLmlla (1~ is applied as a ~ttcrPrc~nn c;n~ from 0.001S to 496 of the com~d tn agueaus med;ium.
l~e present compounds gel~erally provide coloured textile material ~ich s~ws r~od fastness to washi~g, light and heat.
Examples of suitable cllh¢t~tllPntc for Rilys A ar~l D are cyano, hy~roxy, nitro, halo such as fluoro, chloro or hromo, flllrrnclllrhAnyl~ tr1fl '',~1 or alkyl, alkoxy, aryl, arylo~y, heterocycloallcyl, alkylthio, arylthio, l~L~u-. ylthiO, -S4aryl,; -N6Cûalkyl, -~)aryl, -NHSO2aLlcyl, -NE~SO,aryl, -NHS0,arylaL~cyl, -Oa)aL'cyl, -OCûaryl, -C0aL'cyl, -C0aryl, -C0ûalkyl, -C0ûaryl, alkylOO0aryl, -SO,alkyl, -SO2aryl, -SO,arylOE, -NRIR' or -50~NRIR2 i~ which Rl aml R' each ,1 ly is -H, aL~cyl, aryl, a~kylaryl, cycloalkyl a~d-C0aryl or Rl ~5 and R' together with the -N atom to which they are Att::~rho~ fnrm a 5- or C ~ ' ' ri~g such as m~rhrS;nn or rtrr~rt~ttnr Each of the aL~yl, alkc~, aryl, aryloxy, heterocycloal}Lyl, cycloalkyl parts of the cllhqtttllPntC for Ri~gs A an~ D may be optio~ally 51~h~titllt~1 by -OH, -C~, -Cl, -F, -Br, -SO,F, alkyl, aL~y, -OCOûalkyl, -SO,~lkylalkoxy, -ûCOp~nyl, -alkyl~-CO(C~ or -alkylN-CO(CEI~)s allw~ethyl, hy~u~y~Lhyl or phenyl.
Each lkyl ~n the above sllhctttllPntc is pref!~r~hly Cl 1O-alkyl more prefer3bly Cl ~-alkyl, each allcoxy is preferably Cl l~-a~Xoxy more prefer3bly Cl ,-alkoxy, each of which may be straight or bra~hed ~ain SU8STITUTE SHEET (RULE 26~
WO 95/Z1958 2 1 8 0 8 5 2 I t l,. , Alkyl or 2~1koxy, ea~h ryl is pre~er~y }ihenyl or ~hthyl each ryloxy i6 preferAhly pherloxy or ~ .Ll~y, each hetemcycloalkyl is preferably triazolyl, each alkylt_io is prefer~hly Cl ,-Alkylthio, each srylthio is prefer hly phenylthio, each 1~ L~udLylt_io is Ereferahly hon7nthiA7nlylhio Ansl each alkylaryl is proferably Cl~-alkylphenyl especially ~e"--yl, each -COaryl is prefP-~hly -COpherLyl Anr~ each Alkyl, alkoxy, aryl or cycloalkyl may carry arL -SO2F ,ctlhet~tll~nt r ,. ~ l, " .
twc~ adjace~Lt cllhctitl~ontc may _e combined to form a .: ' hetemcyclic ri~y.
r~Of,.r~,l c--hetitll~ntc for Riys A a~Ld D ar_ hy5mxy, chlom, hromo~ flllnrnclllrhnn~l or aryloxy, hetemcycloalkyl, 1~ L~ylth-io each of ~ich is optionally qllhetitllt~ _y -CIEI, -SQF, -O00alkyl, -SO~Elalkylalkoxy, -O~phenyl, -alkylN-CO(CE~)s, -NE}SQar~l or -SO,arylaE;
NRlR' or -SQNRlR' in ~1rhich Rl ~n~ R' each i ~ y is -~, alkyl or ryl each of ~ich is nrt;nn1117y ctlhct~tttt~l hy -SO,F, -CE~, alkoxy or all~yalkyl .
Rc~ri~lly l,.. r_. ,_1 clthctitllc~ntc for Riags A and D ar~
-~EI, (4-SO,F)phenoxy, -N~, (4-~K-3-SO,F)phenyl, -NE'14-SOIFphenyl~, -N~I(3-SC~F~ryl, -NEI(2,4-diSO~Fp}~cLyl), -SQphenyl, (4-SO,F)phenylthio, -(CE~8),OCO(4-SO~Fphenyl), -CO~4-SO,Fphenyl), -N~phenyI and -N~}~3 -~n,rl~,n~,~hF~nyl) llLe ' of FormLla (1) preferahly carry a total of fmm 1 to 3 -SQF gr~s,- more preferahly 1 or 2 -SQF groups and especially 1 -SO,F groups.
'rhe, ~ ' of Formula (1) except for the co~s listed ahove anr~ ~he ~ollowing comEx~L~s l-N- (4-methyl-3-fll--rnc~ yl~l~lyl) l-N-methyl~ ~ N benzyLamino-2-flllnrnclllrhnt 1 ~ N ben_ylamino-2-fl~nrn5~'1rhnnyl~
l-amiro-5-t'l~nrne~lrhnnyl~ , and l-N((4-fllmrns-~lrhnnyl)ben7yl) ~ ,r,; ~_ are novel and ~ Jly form a further feature of t~hA present irLve~Ltion.
A l _r_. ~1 sub-group of compoullds of For~la (1~ ar~ thLose 35 of Forn~la (2~:
/
SUBSTITUTE SHEET (RULE 2~) -W0 95121958 2 ~ 8 ~ ~ 5 2 s k ~R4 RJ O Z
Formula (2) in which:
R1 and R' oA~-h ;~ ly i8 -H, or alkyl, alkylaryl, aryl or -COcLryl ~ptic5~aLly qllhqtitllto~ hy -SO2F, -OH, aL~y or a7kylOH, or -SO3aryl optirn~lly ellhetitllto~; _y -SO2F, -SO3alkylOSO3H or Alkyl;
R3 is -H, -G, -3r, -503F or lkyl, alXylOCOaryl, aryl, CycloAlkyl, heterocycLo_lkyl, alkoxy, a7yloxy, alkylthio, Arylthio, I~L~uelLylthiO or -502aryl each of which is optiorlaLly qllhetitlltorl hy -CIE, alkyl, a7koxy, -OCOOalleyl, -CEI~-CO(CEI2)s, -503NHlkylalkoxy, -503F, -COOAlkyl or -OCOaryl;
Rs is -H, -SO3F, -Cl, -Br, -C~ or aryl or aryloxy oach option~lLy qllhetitllt~ _y -a~, -SO3F or -OCO)alkyl;
or R3 a~ Rs together with the c~C~n atoms to which they _re attach~d form a ' . ' ' h~2terocyclic ring;
Z is -H, -OR1, SR1, -NR1RZ or -COaryl;
Rs an~L R~ oAch ;~ ly is -H, -NO3, -ORl, -~RlR2 or -502F; a~d R' a7ld R7 each ~ l~L~ ,1 ly is -H, -SO2Fs or halo.
~7hore any of the groups ~ .1 hy Rl, R2, R3, Rs or RD is or corLtain aLkyl or aL~coxy ellh~titl~ontq th se are prefer7hly Cl 1O-alkyl or C, ,O-alkoxy, more ,oreferably Cl ,-alkyl or Cl c~-aLlcoxy.
Where 7ry of the gm~ps ,-~ 1 by R~, R3, R3, Rs, Rs or R' is or cont~ aryl or aryloxy cllhctitllontq these are prQe~bLy phenyl or phenoxy ~ere either of Rl or R2 is alkylaryl it is preferably C"~-a7kylzLryl, mDre preferahly henzyl.
The h~2Le~J~y~loalkyl gr~p ~ y R3 is prefora~y l, 2, 4-triazirL-5 -yl .
The hrL~ ylthio 9rCND ~_l.._C_..I_.l by R3 is pre~ ly h~n~.~th; A 7~l1 ylthio .
Where R6 A R7 are hA~ o the hAl o is preferabLy -Cl, -Br or --I a~d ~Dre proferably -Cl.
Where R3 a~ Rs to~ether with the car_on atoms to which t-h-ey are atta~hed _orm a 5 ~ ~ heterocyclic ri7 g thLs is preferably o~
the Formula (3):
SUBSTITUTE SHEET ~RULE 26) WO gS/21958 ~ û 5 2 r ~
o C~N--R9 o Forrnula ~3) in which R' i5 alkyl optio~lly ~-hctit..tG,. by ORl ~erein Rl is as 1._,~;,.1~r."~
def ined.
R9 is pl-efe -Ahly C-l ,-aL7cyl.
Especially ~ r~ ,l r~o~mhs of For~la (2) a~e those in which Rl, R3, R~, Rs, R', R7 and R~ are all -EI, Z is -CE~ and Rl is (4-fll.nrnqnlrhnnyl~phenoxy a71rl in whir~l Rl, R2, R5 R', R' a~ d R' are a7 1 -.1, Z
is -N~13 a~ R3 and R' a7e both 4-fllmlrns7llrhnnyl p_enoxy.
r r;nn~ cin,J r7.;qrr.7-c;nnc o_ the compounds of Formula (1) in which Rlng A a~r~ Ring D a~ e as 1, . ;"l._r", . rlefined; and at least one of Rings A or D ca~ ries directly at least one -SC~F gro~p o_ rarries a c71hctitllr.1~t to which at least one -SO,F ~,LUU~I is attached in aqueous media a~ e novel a~;d form a f~urther feat~re of the present invention. ThQ, ~ t;nnc ty,,oirally .omp ise f ~m 19~ to 30% o_ t~le r~ound of Formula (1) and are preferah~y buffered at a p.~ fmm 2 to 7, 25 nore rrG77GrAhly at a pE~ from p.. ~ 4 to 6.
These r7;cnGrc;nnc may further comprise ;n ~;Gntc co~rGnt;nnAlly used in dyein~ Arr7;rAt;nn~ such as r7;crGrC;ng agents l~or example lirJnnclllrhnnAtGc~ nArhthAlGnr~ su_phonic acid/fnrr--lr7Ghyde or p_enol/rresol/c7-lrhAn;l ;~ acid/fnrmAlr7Ghyde ~ ..1 ,c, ,.,. rt., I ,.. ,l ~, wetti~g a~ents surh as aL~yl aryl etho.~ylates which may be ~llrhnnAtGr~. or ~ .1, i7~ganic salts, de-foamers such as mine~l oil or ~anol, organic liquids an~ ffers. n;crrrC;n~ age~lts ray be preserLt at f~ om 10% to 200% on the weioht of the compound o~ Forn~la (1) .
Wetting agents may be used at from 0.~ to 20~ on the weight of the ~ound o~ For~la (1) . The r~;crGrcinnC mAy be prGpared by bead milliry the compound of Forr[Dula (1) with glass h~r~r7c or sand i71 an ar,lueous medium .
,~rrnrr7;nrg to a fu~ther feature of the present invention there iB prcv~ded a pmcess for the mass rnlnrAtinn of plastics which cull~ises ~ ; ~ J into a plastics material a rompound or mixture thereof which is free fmm water cnlllh;l;cinrJ gmups, of Fos:Dlla (1~ wherei~ Ring A and Ring D are as hGrGinhr~7~nrG def;~ed a r~ at least one of Rirlgs A or D
rarries directly at least one -SO2F r~roup or rArries a cllhct;tllGnt to whir h at least orle -Srj3F r~roup is .~ttached.
SUBSTITUTE SHEEr IRULE 26 WO 95/21958 2 1 8 0 ~ 5 2 The plastics may be selected from polystyrene, acrylics, styrene/acryl nn; tr; 1 P mixtures, acryl nn; trl 1 P/i~lt~; PnP/styrene mixtures, poly~L~-Le, polyether-sulph~e, nylons, rigid PVC (u~VC~ and polypropylene .
S TrLe co! pound may be ;, ~ rl by bleTlding wit~ granules or powdered plastics material by, for exAmple, dry tumbling or high-speed m~xing followed by irjection moulding on a scr~w machinP or by coTventianal ~ J torhn;rlllPq Tho present ~yes ~enerally dissolve or disperse readily iTL _ot plastics melt a~d provide bright rnlrrAt;rn r~enerally wit_ good clarity and rl~od light fastTIess.
The plastics materials whPn coloured with t_e above ~yes fo~m a further feature of the preseTLt iTlVentiOn.
The compounds of Foramla (1~ may be obtain_d by usual methr~q fcr thP rr~ArAt~rn of _~ compounds such as by oxidation of = 1 ~ or ~lhct;tllto~ 4 with 1 ~ ~;rhrr P i~
sulphuric acid or by reaction of a phthalic anhydride with beT~7ene or a qllhqt~l-tP~ ben-7ene in t_e prese~Lce of ~1 chloride followed by ring closure in hot sulphuric acid.
Fl~nrnqlllrhrnyl rroups may be i, l .." .~ ~.1 iT~to the compt7L~nds of For~lae (1~ or ~2~ by methods geTIerally a-vailable in the l;torAtllrP
For example reaction of a compound of Forn~lae ~1~ or ~2~ with rhlnrnnllrhrn;r acid optio:~ally in t_e preseTIce of dimethyl ~P And thionylrhlnr;~lP at a i ~ of fr~ 30C to 100C gives the rhlnrnnllrhnnyl .l~iV,,Liv~. The rhlnrnnllrhrnyl ~ivcLLiv~ may be rejLcted in boiliTlg aqueous media with 1 fluoride to give the fllmrnnllrhnnyl d=Liv~Liv~.
1 ;v:ly a cpound of FormL~ or ~2~ may be qlllrhnn:ltPrl with sulrhuric acid or oleum to give the sulphr~ic acid d~iv~Liv~: which may be coTlverted to the rhlnrnclllrhnnyl d~iv-Liv~ by reactirn, eithP~ of the free acid or aTL ir~rganic salt thereof, with thionylrhlnr;~lP ~t;nnAlly in the presence o~ a rhl ....lJ, ~l ..."~ compauDd such as l1, ~L1 ~ ~ oxychl~ or l~ rPnt~rhlrr;~o n an or~3anic liquid such as an aromatic lly~ at a t , of from 20C to 110C. The rhlnrnqlllrhnnyl ~ivc-Liv: may theTl be cr~verted to the flllnmnllrhnnyl d~Liv.~Liv~ as rloqrr;hPrl above.
The c3rpounds of For~lae ~1~ a~d ~2~ are useful fr~r the rnlnrAtirn of synthetic textile materials rArt;r~ rly polyester textile materiAls a~d fibre bleTIds t~ereof to which they impart colours which have ex~ellent wet aTld light fastness rrrrortiPq.
The comp~ds of For~lae ~1) and ~2) ar~ also useful for the mass rnlnr~t;rn of plastics as floqrr~hP~ a~ove and impart bright colours generally with good clarity alld 1;.l,l r=~ .,c~
The i~tion is further illllqtrAtP~ ky the followi~g Examples .
SUBSTITUTE SHEET (RULE 26) _ . .. .
WO 9~/219~8 r lP 1 ~n:~r~ti nn of 1 A '~ 2- ~4-fllmrnqnlnhnnvlnhPnn~V)_~ Jl~t To a mix~ure of 1 q hydmxy-2- (4-~-hln7-ne--lrhnnYlF~cy~ r~ -- (2 p~t5) and 1,~-di =e (25 parts), stirring at ambient t-, , waS RA~lP~ a solution of pntRI fluoride (0.6 parts) in water (s pRrts~ . The mixture was heated to 60C a~d s~irred at this i , for 20 minutes. After cooling to 0-5C, t~ pmduct was isolated by ~;lt7-Rtinn, was_ed with water and dried at 50C to yield: 1 ~ hydmxy-2-(4-f1"n7ne"~ yl~Y)~ (1.6 parts). Amax = 515.0um ~C~2Cl2) r 1P 2 l?r~nR~Rtinn of 1,5-~17hv~cv-2-(4l-h~rn~rv-3~-f~1~nslll~ vlLJi~eLIvl- 4,8-rli~ ~ . .
chln7-neRllnhnni, acid (11.4 pRrtS) was stirred at mom while 1, 5 -d; hydroxy- 2- ~4 ' -lLy~y~LleLLy l ) -4, 8 -(o 5 pRrtS) was RrqtqPr7 slowly over 30 mins. A~ter stirring for 30 minul~es thionyl chloride (2.5 p rts) was added. The reaction mixture was stirred at 40C or 3 hours. Cn ccoling the reaction mixture was poured i~ltO ice/water a~d the resulti~ agueaus ~lerPn~inn was filtered to yield the sulphonyl chloride l~LivaLive (0.49 parts).
The sulpl~nyl chloride leLivcLLive ~1.6 p_rts) was added to 1,4-dioxane (94 p_rta) at mom ~ - before adding L
fluoride (5.2 parts) in water (111 p_rts) . After heating at 60C for 4 hours the mixture waa cooled, filtered and dried to yield 1,5-dihydrc~cy-2-(4'hydroxy-3'-~ nrne--lrhnnylphenyl 4,8-~ (1.02 psrts). A ma~c - 587nm, 629nm.
Dyes of ~70rn ~1a(2) in which R' and R7 are -1~ were prepared by the ~ l _ o~ Exasple 2:
3s R7~R3 Rs O z Fom u~a (2) a~d these are ~ e~rl in ~able 1:-SUBSTITUTE SHEEr l~ULE 26 W0951219~8 ? ~ 8 ~ 8 ~ "~
.~
o U o X C, ,~ ~, N r ~ C~
~r .
L L
", ; L' ~
CC CC 3 0 ~
0 5 Z Z 3: 0 U O Z
C
.
C C~
1:~ 2 ~ ~ '~ ~r ~ C ~, ~ C _ _ _ ~ ~ ~ 2 ~ 3 r T ~ ~ 5 = ~r .
C~
c c c c ~ .r c O .. ~
SUBSTITU~E SHEEr tRULE 26) WO9S/21958 2 1 8~ ~2 lo P~
E~r e~urples of dyes made see I~le 1.
r- 18 Pr~r~tirn of 1-smino-2-fll1nrnc-l~nhnnvl-4- (N-nh~n l) . ~
S 1-Ami~o-(N-phenyl~ _ 2-sulpho~ic iacid (2.5 parts~ was heated 1 pyridine (100 parts~ at reflux for 2 hours. The reaction mi~cture wa~ filtered a~d the pyrirqin~ removed on a rotary ev~ul IL~L to yield 2.3 parts of t_e pyrirlin:Lum salt.
The pyrir~irium salt (1 part~ vas heated at 75C for 4S
mi~utes in K~Cl (20 par~s~ . On cool~y the reaction mixture was poured illto ice/ivater fil~ered an~ the resultiDg solid was washed 5ev~al times with water. me sulrhonyl chloride was heated at 100C for 3 hours w~th L ' fluoride (3 parts~ in 1 4-di = (47 parts~/water (22 parts~
After coolily the reaction mixture was filtered and the solid obtained washed with wiqter to yield 1-ami~o-2-fll-rim~-lrh nyl-4-(N-phenyl~ ` nnn~ (0.2 p rts~ .
~ 1f' 19 i prPn=r=tinn of l-alTiLno-2-fllmmc llnhnnvl-4- ~N- (3-sul~honvlethvl sul~hc7rlic Ari 1~nh-~nvl i nnn~
1-Amino -4- (N- ( 3 - sulphonylethyl ~-1 rhnn; r acid) phenyl ~ amino--2-sulphonic acid (1.2 parts~ was heatel to reflux in -pyridine (814 parts~ _or 24hours. me pyridine was removed by rou~y evc~L~L L a~d the ~esulting solid washed with petroleum ether (b. pt.
60-80C~to give the dipyridinium salt which was dissolved in ~MF (972 parts~ and thionyl chloride (340 parts~ was ad~ed dropwise. me mixture was heated at 80C ~or 4-5 hours cooled poured into water alld filtered to ive the sulphonyl chloride ~iv-~iv=.
me sulphonyl chloride leLivcL~Lve (1.76 parts) was heated at 80C for 18 hours with fluoride (13.5 parts~ in 1 4-dioxan (468 parts)/water (555 parts~ . ~fter cooling the solvents were removed on a rotary ev~l~ .l . to yield a solid which was washed with watOE ~efore kei~ig dissolved in acetone and screened throu~h silica. me acetone was removed to yield 1-amino-2-f1-1nmq -1rhrnyl-4- (N- (3-sulphonylethy~ rhnnir acid)phenyl - i~ _ ril2Dm.
r 1 f 20 ii~n~l 21:
pr ni~r~tinn of l-amino-2-fllmrnqnlnhnnvl-4- (N- (4-flllnrnclllnhnnvl)nhl~nvl) and 1 -2-flllnm~lllnhn 4- (N- (2 4- 1i fllmmcnlnhnnvl)~henvl~ ~.
l-Amino-2-rhlnrn~-lrhnnyl-4- (N-phenyl) nnn~ (1 }) was added to a stirred mixture of rh1nrn~11rhnnir acid (35 parts) and thionyl c-hloride (8 parts~ a~d heated at 65C for 2.5 hours. After cooling to room t~ the reaction mixt~lre was po~2 ed ;ntn r 45 ice/water and filtered to yield a solid which was washed several times SUBSTITUTE SHEET (RULE 26) W09St'~1958 2 1 8 ~ ~ 5 ~ I ~1. . , wit_ water. Ihe solid was heated at 100C _or 2 hours with ~ ' fluoride (40 parts) in 1,4-diosn (480 parts~/water (440 parts~. On ccoling, th~ reaction mixture was filtered and the solid obtained washed with water to gil~e l-=o-2-fll~nrnnllrhn"yl-4-(N-(4-S fllmrnnllrhnnyl~phenyl~ a~d l-amino-2-fllmrnnllrhnn 4-(N-(2,4-~l;flllnrnnllrhnnyl~p~nyl~ = 534nm. The ~s may be ~PrPr-AtPr1 1' rAlly r 1P 22 pn~l 23 pr~nprAtinn of 1~5-dihv~ro7cv-2~6-~l;nlmrnn~lnhnnvl-4~8-Al111; nnnP and 1.5-dih~drwcv-2-flvnr~snl~hr,nVl-4,8-~ 6 rh1 1 ~
1,5-Di=o-3,7-~l;n-l~ ,ll",.. ,r", (2.7 parts~ was heated in pyri~;nP (10 parts~ at reflux for 2 hours. The solution was th~n filtered and thle pyridine removed on a rotary eVW~LCLLUL to yield the dipyridinium salt (2.5 parts).
~he pyri~linium salt (0.47 parts) was heated at 75C for 9 hours in PCC13 (107 parts). After addi~g toluene (235 parts) the reacticn mixture was heated at 120C for 3 hours. After cooling, the reaction mixture was filtered and the resultillg solid sulphonyl chloride was was_ed sevOEPl times with water. The sulphcnyl chloride was heated at 100C for 3 hours with, ' flucride (1.7 parts) in 1,4-di~ (59 parts) . After cooling, the reaction mixture was filtered a~d the solid obtained washed with water to give 1~5-dihydrcncy-2~6-~l;nllnrn 4,8--i; - nnnr and 1~s-dihydrcocy-2-flllnrnnllrhrnyl-4~a-diamin 6-rhl~ . Ihe product was a mixture of 22 a~d 23, with 23 ~eing th~ ma~or _ of the mixture.
~ lw 24:
p~nprwtirn of 1 ' ~ (N-(4-fll~nrnnllnhnnvl)~henv3~) ;II I.~IIIll _~lll;ll~ IIG
(3.3 parts), sodium acetate (5 parts), cupric acetate (0.5 parts~ and sulphanilyl fluoride (4 parts~
were stirred in o-~l;rhl,,.~.l~. . ~ (88 parts) at 1~0C for 30 hours. The solution was allcwed to cool and filtered, the solid was washed with 35 WatOE several times to give l-amino-4-(N- (4-flllnrnnllrhnnyl~phenyl) r 1~ 7sprPnRrRtinn of 1 ~ hvArn~-2- (4-40 fllmmnll l"" vl"l,_" "v)~"ll .. ";, A m~xutre o~ l-amino-4-hy~roxy-2-~ y_"l l", l,;, " _ (0.2g) was stirreA
aver~ight with flllnrnnllrhnn;r acid (10c~) and poured onto ice. The rr~rinitRt~i solid was rnll~rt~ by filtr~tinn ~nA washed with water and dried to gi~e l-amino-4-hy~r~Ly-2-phen~y ,."l 1, ~ (0.17g, 70'6) .
SUBSTITUTE SHEET tRULE 26~
sy~thetic textile materials, to ~ynt_etic textiles when colc~red, to a process for the mass rnlnr~t;nn of plastics, to plastics when coloured to certa~r novel ~ dyes and to, tinnc . ~ .J
~ dyes.
ccording to t_e 7~resent invention there is provided a process for colouring a synthetic textile material or f~ore Jlend t_ereof which cc~prises applying to the synthetic textile material a compld of Fora~la ( 1 ~:
Forrnula (1 wherein Ring A and Ring D æe nrt~nn~lly ~lh~st~tlltp~ and at least one of ~ily A
or Ring D carries at least one -SO,F group except for 2- [(9,l0-d;hydro-g,3:0-dioxo-l--.,1 l,._, ~yl)amino] -oth~n~clllrhnny~fllln 2-t(9,10-d;hydro-9,10-dloxo-2-~ y~ no]-~th:~noclllrhnnylfllmr;~
2,2'-[(9,10-dihydro-9,10-dioxo-1,4-~.,11"~ ,l;yl)diimino]h;c~h~n Sulp7~onyl flllnr;~O, 25 2,2'-[(9,10-dihycro-9,10-dioxo-1,5-,.. 1l.. _. .. ~.l;yl)diimino]h;c~th~no sul ~honylfluoride, 2,2'- [(9,10-dihydro-2-methoxy-9,10-dioxo-1,4-r...l 1~ ;yl)diimino) h;coth~noclllrhnnylflllnr;~9~
2 - [ (4- (~z;oylamino) - 9, 10-dihydro- 9 ,10-dioxo-l-- .I l,, _. -. yl] amino]~th~noclllrhnnylfllmr;~o 2- [ (9,10-dihydro-4- (met~ylamino) -9, 10-dioxo-l-_. .1 7" ,.. -"yl] amino] eth ne s~lphonyl fl llnr; ~O
7~;ffc-ront, ' of For~ la (l) mi~y ~e mixed or the cc~o~ s of Formllla (1) may ~e mixed with dyes which do not contain ~n -SO,F group, suc~ mixtures æe a feature of the prese~t invention.
The mixtures l;ay 70e simple physical mixtures or mi~y ~e mixed cryst~l s ~ormod ~or exallple ~y co-cry~ tAl l i q~t~ nn Such mixtures gener lly show , v~ in dyeing properties. Crystallirle ~;;~;r~t,nnc 0_ compaun~s of Formula (1~ exist and it is intended that the present 'o~;n~t;nn illcl7~des such crystalline ~;f;r~t~nn~ whic7l may ~or e~3mple ~e fo~med hy heat tro~trlont, SUaSTlTUTE SHEET (RULE 26) _ _ WO 95/21958 ~ 5 - /
2~ 52 2 n-T to a ~urther ~eatT~re o~ the presQ-nt ~ven~ion there is pmYided a pmcefis for colouring a polyester textile Trateri 1 or fibre blend t_ereof which comprises applYiTlg to t_e polyester textile material 2-t(9,10-dihYdm-9,10-dioxo-1~ T,...~ yl)aTr~no]-Pth~nPQllirhnnylf7llnr~rlp~
2-[(9,10-dihYdm-9,10-dioxo-2-,."~ ,,yl)a~ no]-pthAnc~Qlllrhnnylflllnr~
2,2'-[(9,lO-dihYdm-9,10-dioxo-1,4-~ l;yl)oiimi~o3--isethAne alllrhnnylf~llnr~P, 2,2'-[(9,10-dihYdm-9,10-dioxo-1,5-,."11 .,. - ~l;yl)diimino~biseth ne 51.1ph0nYl flllnr~P, 2,2'-[~9,lO-dihYdm-:2-methoxy-9,10-dioxo-1,4-A.. ll,.A.. ~ ;yl)dii) h~ QPth:lnpclllrhnnyl flllnr~lP, 2- ~ (4- (benzoYlaTrino) ~9,10-dihY~m-9,10-dioxc-1-,. ,l 1".,.,, yl]aTr~no]
PthAnPClllrhnnyl flllnr~-lo, 2- [ (9,10-dihYdm-4- (meth--ylaTrino) -9, 10-dioxo-1-~ yl] aTr~no~ eth~rP
sulph~nYl f l 1 1nr~ rlP .
The Fresence of one or Trore -SO.F gmups in a dye molecule generally impmYes t~le Fr~7Prt~Pc of tùat dye a~d confers cll~r~c~n~ly good wet-fastness a~d light-fastness rmrPrti~a.
The synthetic textile material Tray be selected fmm secondarY
cellulose acetate, cellulose tr~ArPtAtP~ Folyamide, polyacrYlonitrile ~d arT~rratic polyester. The synt_etic textile material is Fre-ferah-ly FlYamide or amTratic polYester, such as pol,' ', lene adiFamide or Folyethylene tPrPrht~lAlAtp more preferably =tic Folyester and especially poly-ethlene tPrPrhthAlRtP~ Pibre blPn~Q my comprise mixtures of ~;ffPrPnt synthetlc textile materials or m~CtureS of synthetic and nat~r-Al textile --~Pri~lc. Preferred fibre bLendfi are those of Folyester-cellulose sUch- as Folyester-cotton. The textile materials or hler~ds t_ereof may be in the ~orm of filaments, loose fibres, yarn, woYen or knitted fis.
The dYes of For~la (1) FrefPr~hly haYe low solT~bility in water, tYpiC lly less th~n 1~6 preferabLy lesg them 0.59~ alld esperiAlly less than 0.296 Qnlllhil;ty in water. The dyes of For~la (1) are t~h-us free fmm water snlllhil;Qin~ Qs such as -SO,II, -CO2i/, -PO,Il and LL~:L I IA ' y amino .
The dres of Formula (1), optionally in conjunction with other disperfie dyes Tray be applied to the sy~thetic textile materials or fibre blPn~C thereof by Trethods which are conYentionally employed in dyeing disFerse dyes to such mAtPriAlC a~d fibre blentis. For e~mple, the dyes of FormuLa (1) in the form of an aqueous rl;crPrQ~nn may be a~?pliel by dyeiny, padding or printing ~L~ a~e:S ufiing the rnn~;t;nnc and additiYes conY~ntirnAlly used in carrying out such pmcesses.
The pmcess rnnrlitirnQ Tray be selected fmm t_e following:
i) exhaust dyei~y at a plI of fr~m 4 to 6.5, at a L _ of fr~n 125C to 140C for fmm 10 to 120 minutes and u~der a pressure of fmm 1 to 2 bar, a ~ All may be opti~ally be added SUBSTITUTE SHEET (RULE 26~
WO 95~1958 2 1 8 0 8 5 2 dyeing at a pEl of ~rom 4 to 6.5, at a; , of from 190C to 225C for from 15 secon~s to 5 m~utes, a migration inhiitor may option lly be added;
iii~ printing direct at a r~ of from 4 to 6.5, at a i , of from 5 160C to 185C for 4 to 15 minutes for high L , ' steami~g, or at a t, of from 190C to 225C for 15 seoon~s to 5 minutes for Ake fixation with d~y h-eat or at a t , of from 120C to 140C a~d 1 to 2 bar for 10 to 45 m~nutes for pressure steam~Ilg, wetting agents a~l th;rl-PnPrc (such as ~lginates~ of from 5 to 100S by weight of the dye may be optionally be ad~ed;
iv~ ~t~$rh~e rri~ting (hy paddirlg the dye onto t_e textile material, dry~ng nd uv~ ) at a pE of from 4 to 6.5, migration ,nh;h-tnrc al~d thlrlopn~rc may option lly he added;
v~ carrier dyei~ at a pH of from 4 to 6.5, at a L , ' of from 95C to 100C usillg a carrier suc_ as met_yln~rhth;llPnP, diphPnylamine or 2-r~enylphenol, ~r~ may optionally ~e added; and Vi~ ;r dyeiIy of acetate, trlArPt~tP and nylon at a pE~ of from 4 to 6.5, at a t, ' of 85C for acetate or at a;
of 90C for tro~rPt~tP and nylon for frc~m 15 to 90 miI~utes, ~r ~ may opt rn~lly he added.
In all t_e a~ove ~u~____ the compound of ForLmlla (1~ is applied as a ~ttcrPrc~nn c;n~ from 0.001S to 496 of the com~d tn agueaus med;ium.
l~e present compounds gel~erally provide coloured textile material ~ich s~ws r~od fastness to washi~g, light and heat.
Examples of suitable cllh¢t~tllPntc for Rilys A ar~l D are cyano, hy~roxy, nitro, halo such as fluoro, chloro or hromo, flllrrnclllrhAnyl~ tr1fl '',~1 or alkyl, alkoxy, aryl, arylo~y, heterocycloallcyl, alkylthio, arylthio, l~L~u-. ylthiO, -S4aryl,; -N6Cûalkyl, -~)aryl, -NHSO2aLlcyl, -NE~SO,aryl, -NHS0,arylaL~cyl, -Oa)aL'cyl, -OCûaryl, -C0aL'cyl, -C0aryl, -C0ûalkyl, -C0ûaryl, alkylOO0aryl, -SO,alkyl, -SO2aryl, -SO,arylOE, -NRIR' or -50~NRIR2 i~ which Rl aml R' each ,1 ly is -H, aL~cyl, aryl, a~kylaryl, cycloalkyl a~d-C0aryl or Rl ~5 and R' together with the -N atom to which they are Att::~rho~ fnrm a 5- or C ~ ' ' ri~g such as m~rhrS;nn or rtrr~rt~ttnr Each of the aL~yl, alkc~, aryl, aryloxy, heterocycloal}Lyl, cycloalkyl parts of the cllhqtttllPntC for Ri~gs A an~ D may be optio~ally 51~h~titllt~1 by -OH, -C~, -Cl, -F, -Br, -SO,F, alkyl, aL~y, -OCOûalkyl, -SO,~lkylalkoxy, -ûCOp~nyl, -alkyl~-CO(C~ or -alkylN-CO(CEI~)s allw~ethyl, hy~u~y~Lhyl or phenyl.
Each lkyl ~n the above sllhctttllPntc is pref!~r~hly Cl 1O-alkyl more prefer3bly Cl ~-alkyl, each allcoxy is preferably Cl l~-a~Xoxy more prefer3bly Cl ,-alkoxy, each of which may be straight or bra~hed ~ain SU8STITUTE SHEET (RULE 26~
WO 95/Z1958 2 1 8 0 8 5 2 I t l,. , Alkyl or 2~1koxy, ea~h ryl is pre~er~y }ihenyl or ~hthyl each ryloxy i6 preferAhly pherloxy or ~ .Ll~y, each hetemcycloalkyl is preferably triazolyl, each alkylt_io is prefer~hly Cl ,-Alkylthio, each srylthio is prefer hly phenylthio, each 1~ L~udLylt_io is Ereferahly hon7nthiA7nlylhio Ansl each alkylaryl is proferably Cl~-alkylphenyl especially ~e"--yl, each -COaryl is prefP-~hly -COpherLyl Anr~ each Alkyl, alkoxy, aryl or cycloalkyl may carry arL -SO2F ,ctlhet~tll~nt r ,. ~ l, " .
twc~ adjace~Lt cllhctitl~ontc may _e combined to form a .: ' hetemcyclic ri~y.
r~Of,.r~,l c--hetitll~ntc for Riys A a~Ld D ar_ hy5mxy, chlom, hromo~ flllnrnclllrhnn~l or aryloxy, hetemcycloalkyl, 1~ L~ylth-io each of ~ich is optionally qllhetitllt~ _y -CIEI, -SQF, -O00alkyl, -SO~Elalkylalkoxy, -O~phenyl, -alkylN-CO(CE~)s, -NE}SQar~l or -SO,arylaE;
NRlR' or -SQNRlR' in ~1rhich Rl ~n~ R' each i ~ y is -~, alkyl or ryl each of ~ich is nrt;nn1117y ctlhct~tttt~l hy -SO,F, -CE~, alkoxy or all~yalkyl .
Rc~ri~lly l,.. r_. ,_1 clthctitllc~ntc for Riags A and D ar~
-~EI, (4-SO,F)phenoxy, -N~, (4-~K-3-SO,F)phenyl, -NE'14-SOIFphenyl~, -N~I(3-SC~F~ryl, -NEI(2,4-diSO~Fp}~cLyl), -SQphenyl, (4-SO,F)phenylthio, -(CE~8),OCO(4-SO~Fphenyl), -CO~4-SO,Fphenyl), -N~phenyI and -N~}~3 -~n,rl~,n~,~hF~nyl) llLe ' of FormLla (1) preferahly carry a total of fmm 1 to 3 -SQF gr~s,- more preferahly 1 or 2 -SQF groups and especially 1 -SO,F groups.
'rhe, ~ ' of Formula (1) except for the co~s listed ahove anr~ ~he ~ollowing comEx~L~s l-N- (4-methyl-3-fll--rnc~ yl~l~lyl) l-N-methyl~ ~ N benzyLamino-2-flllnrnclllrhnt 1 ~ N ben_ylamino-2-fl~nrn5~'1rhnnyl~
l-amiro-5-t'l~nrne~lrhnnyl~ , and l-N((4-fllmrns-~lrhnnyl)ben7yl) ~ ,r,; ~_ are novel and ~ Jly form a further feature of t~hA present irLve~Ltion.
A l _r_. ~1 sub-group of compoullds of For~la (1~ ar~ thLose 35 of Forn~la (2~:
/
SUBSTITUTE SHEET (RULE 2~) -W0 95121958 2 ~ 8 ~ ~ 5 2 s k ~R4 RJ O Z
Formula (2) in which:
R1 and R' oA~-h ;~ ly i8 -H, or alkyl, alkylaryl, aryl or -COcLryl ~ptic5~aLly qllhqtitllto~ hy -SO2F, -OH, aL~y or a7kylOH, or -SO3aryl optirn~lly ellhetitllto~; _y -SO2F, -SO3alkylOSO3H or Alkyl;
R3 is -H, -G, -3r, -503F or lkyl, alXylOCOaryl, aryl, CycloAlkyl, heterocycLo_lkyl, alkoxy, a7yloxy, alkylthio, Arylthio, I~L~uelLylthiO or -502aryl each of which is optiorlaLly qllhetitlltorl hy -CIE, alkyl, a7koxy, -OCOOalleyl, -CEI~-CO(CEI2)s, -503NHlkylalkoxy, -503F, -COOAlkyl or -OCOaryl;
Rs is -H, -SO3F, -Cl, -Br, -C~ or aryl or aryloxy oach option~lLy qllhetitllt~ _y -a~, -SO3F or -OCO)alkyl;
or R3 a~ Rs together with the c~C~n atoms to which they _re attach~d form a ' . ' ' h~2terocyclic ring;
Z is -H, -OR1, SR1, -NR1RZ or -COaryl;
Rs an~L R~ oAch ;~ ly is -H, -NO3, -ORl, -~RlR2 or -502F; a~d R' a7ld R7 each ~ l~L~ ,1 ly is -H, -SO2Fs or halo.
~7hore any of the groups ~ .1 hy Rl, R2, R3, Rs or RD is or corLtain aLkyl or aL~coxy ellh~titl~ontq th se are prefer7hly Cl 1O-alkyl or C, ,O-alkoxy, more ,oreferably Cl ,-alkyl or Cl c~-aLlcoxy.
Where 7ry of the gm~ps ,-~ 1 by R~, R3, R3, Rs, Rs or R' is or cont~ aryl or aryloxy cllhctitllontq these are prQe~bLy phenyl or phenoxy ~ere either of Rl or R2 is alkylaryl it is preferably C"~-a7kylzLryl, mDre preferahly henzyl.
The h~2Le~J~y~loalkyl gr~p ~ y R3 is prefora~y l, 2, 4-triazirL-5 -yl .
The hrL~ ylthio 9rCND ~_l.._C_..I_.l by R3 is pre~ ly h~n~.~th; A 7~l1 ylthio .
Where R6 A R7 are hA~ o the hAl o is preferabLy -Cl, -Br or --I a~d ~Dre proferably -Cl.
Where R3 a~ Rs to~ether with the car_on atoms to which t-h-ey are atta~hed _orm a 5 ~ ~ heterocyclic ri7 g thLs is preferably o~
the Formula (3):
SUBSTITUTE SHEET ~RULE 26) WO gS/21958 ~ û 5 2 r ~
o C~N--R9 o Forrnula ~3) in which R' i5 alkyl optio~lly ~-hctit..tG,. by ORl ~erein Rl is as 1._,~;,.1~r."~
def ined.
R9 is pl-efe -Ahly C-l ,-aL7cyl.
Especially ~ r~ ,l r~o~mhs of For~la (2) a~e those in which Rl, R3, R~, Rs, R', R7 and R~ are all -EI, Z is -CE~ and Rl is (4-fll.nrnqnlrhnnyl~phenoxy a71rl in whir~l Rl, R2, R5 R', R' a~ d R' are a7 1 -.1, Z
is -N~13 a~ R3 and R' a7e both 4-fllmlrns7llrhnnyl p_enoxy.
r r;nn~ cin,J r7.;qrr.7-c;nnc o_ the compounds of Formula (1) in which Rlng A a~r~ Ring D a~ e as 1, . ;"l._r", . rlefined; and at least one of Rings A or D ca~ ries directly at least one -SC~F gro~p o_ rarries a c71hctitllr.1~t to which at least one -SO,F ~,LUU~I is attached in aqueous media a~ e novel a~;d form a f~urther feat~re of the present invention. ThQ, ~ t;nnc ty,,oirally .omp ise f ~m 19~ to 30% o_ t~le r~ound of Formula (1) and are preferah~y buffered at a p.~ fmm 2 to 7, 25 nore rrG77GrAhly at a pE~ from p.. ~ 4 to 6.
These r7;cnGrc;nnc may further comprise ;n ~;Gntc co~rGnt;nnAlly used in dyein~ Arr7;rAt;nn~ such as r7;crGrC;ng agents l~or example lirJnnclllrhnnAtGc~ nArhthAlGnr~ su_phonic acid/fnrr--lr7Ghyde or p_enol/rresol/c7-lrhAn;l ;~ acid/fnrmAlr7Ghyde ~ ..1 ,c, ,.,. rt., I ,.. ,l ~, wetti~g a~ents surh as aL~yl aryl etho.~ylates which may be ~llrhnnAtGr~. or ~ .1, i7~ganic salts, de-foamers such as mine~l oil or ~anol, organic liquids an~ ffers. n;crrrC;n~ age~lts ray be preserLt at f~ om 10% to 200% on the weioht of the compound o~ Forn~la (1) .
Wetting agents may be used at from 0.~ to 20~ on the weight of the ~ound o~ For~la (1) . The r~;crGrcinnC mAy be prGpared by bead milliry the compound of Forr[Dula (1) with glass h~r~r7c or sand i71 an ar,lueous medium .
,~rrnrr7;nrg to a fu~ther feature of the present invention there iB prcv~ded a pmcess for the mass rnlnrAtinn of plastics which cull~ises ~ ; ~ J into a plastics material a rompound or mixture thereof which is free fmm water cnlllh;l;cinrJ gmups, of Fos:Dlla (1~ wherei~ Ring A and Ring D are as hGrGinhr~7~nrG def;~ed a r~ at least one of Rirlgs A or D
rarries directly at least one -SO2F r~roup or rArries a cllhct;tllGnt to whir h at least orle -Srj3F r~roup is .~ttached.
SUBSTITUTE SHEEr IRULE 26 WO 95/21958 2 1 8 0 ~ 5 2 The plastics may be selected from polystyrene, acrylics, styrene/acryl nn; tr; 1 P mixtures, acryl nn; trl 1 P/i~lt~; PnP/styrene mixtures, poly~L~-Le, polyether-sulph~e, nylons, rigid PVC (u~VC~ and polypropylene .
S TrLe co! pound may be ;, ~ rl by bleTlding wit~ granules or powdered plastics material by, for exAmple, dry tumbling or high-speed m~xing followed by irjection moulding on a scr~w machinP or by coTventianal ~ J torhn;rlllPq Tho present ~yes ~enerally dissolve or disperse readily iTL _ot plastics melt a~d provide bright rnlrrAt;rn r~enerally wit_ good clarity and rl~od light fastTIess.
The plastics materials whPn coloured with t_e above ~yes fo~m a further feature of the preseTLt iTlVentiOn.
The compounds of Foramla (1~ may be obtain_d by usual methr~q fcr thP rr~ArAt~rn of _~ compounds such as by oxidation of = 1 ~ or ~lhct;tllto~ 4 with 1 ~ ~;rhrr P i~
sulphuric acid or by reaction of a phthalic anhydride with beT~7ene or a qllhqt~l-tP~ ben-7ene in t_e prese~Lce of ~1 chloride followed by ring closure in hot sulphuric acid.
Fl~nrnqlllrhrnyl rroups may be i, l .." .~ ~.1 iT~to the compt7L~nds of For~lae (1~ or ~2~ by methods geTIerally a-vailable in the l;torAtllrP
For example reaction of a compound of Forn~lae ~1~ or ~2~ with rhlnrnnllrhrn;r acid optio:~ally in t_e preseTIce of dimethyl ~P And thionylrhlnr;~lP at a i ~ of fr~ 30C to 100C gives the rhlnrnnllrhnnyl .l~iV,,Liv~. The rhlnrnnllrhrnyl ~ivcLLiv~ may be rejLcted in boiliTlg aqueous media with 1 fluoride to give the fllmrnnllrhnnyl d=Liv~Liv~.
1 ;v:ly a cpound of FormL~ or ~2~ may be qlllrhnn:ltPrl with sulrhuric acid or oleum to give the sulphr~ic acid d~iv~Liv~: which may be coTlverted to the rhlnrnclllrhnnyl d~iv-Liv~ by reactirn, eithP~ of the free acid or aTL ir~rganic salt thereof, with thionylrhlnr;~lP ~t;nnAlly in the presence o~ a rhl ....lJ, ~l ..."~ compauDd such as l1, ~L1 ~ ~ oxychl~ or l~ rPnt~rhlrr;~o n an or~3anic liquid such as an aromatic lly~ at a t , of from 20C to 110C. The rhlnrnqlllrhnnyl ~ivc-Liv: may theTl be cr~verted to the flllnmnllrhnnyl d~Liv.~Liv~ as rloqrr;hPrl above.
The c3rpounds of For~lae ~1~ a~d ~2~ are useful fr~r the rnlnrAtirn of synthetic textile materials rArt;r~ rly polyester textile materiAls a~d fibre bleTIds t~ereof to which they impart colours which have ex~ellent wet aTld light fastness rrrrortiPq.
The comp~ds of For~lae ~1) and ~2) ar~ also useful for the mass rnlnr~t;rn of plastics as floqrr~hP~ a~ove and impart bright colours generally with good clarity alld 1;.l,l r=~ .,c~
The i~tion is further illllqtrAtP~ ky the followi~g Examples .
SUBSTITUTE SHEET (RULE 26) _ . .. .
WO 9~/219~8 r lP 1 ~n:~r~ti nn of 1 A '~ 2- ~4-fllmrnqnlnhnnvlnhPnn~V)_~ Jl~t To a mix~ure of 1 q hydmxy-2- (4-~-hln7-ne--lrhnnYlF~cy~ r~ -- (2 p~t5) and 1,~-di =e (25 parts), stirring at ambient t-, , waS RA~lP~ a solution of pntRI fluoride (0.6 parts) in water (s pRrts~ . The mixture was heated to 60C a~d s~irred at this i , for 20 minutes. After cooling to 0-5C, t~ pmduct was isolated by ~;lt7-Rtinn, was_ed with water and dried at 50C to yield: 1 ~ hydmxy-2-(4-f1"n7ne"~ yl~Y)~ (1.6 parts). Amax = 515.0um ~C~2Cl2) r 1P 2 l?r~nR~Rtinn of 1,5-~17hv~cv-2-(4l-h~rn~rv-3~-f~1~nslll~ vlLJi~eLIvl- 4,8-rli~ ~ . .
chln7-neRllnhnni, acid (11.4 pRrtS) was stirred at mom while 1, 5 -d; hydroxy- 2- ~4 ' -lLy~y~LleLLy l ) -4, 8 -(o 5 pRrtS) was RrqtqPr7 slowly over 30 mins. A~ter stirring for 30 minul~es thionyl chloride (2.5 p rts) was added. The reaction mixture was stirred at 40C or 3 hours. Cn ccoling the reaction mixture was poured i~ltO ice/water a~d the resulti~ agueaus ~lerPn~inn was filtered to yield the sulphonyl chloride l~LivaLive (0.49 parts).
The sulpl~nyl chloride leLivcLLive ~1.6 p_rts) was added to 1,4-dioxane (94 p_rta) at mom ~ - before adding L
fluoride (5.2 parts) in water (111 p_rts) . After heating at 60C for 4 hours the mixture waa cooled, filtered and dried to yield 1,5-dihydrc~cy-2-(4'hydroxy-3'-~ nrne--lrhnnylphenyl 4,8-~ (1.02 psrts). A ma~c - 587nm, 629nm.
Dyes of ~70rn ~1a(2) in which R' and R7 are -1~ were prepared by the ~ l _ o~ Exasple 2:
3s R7~R3 Rs O z Fom u~a (2) a~d these are ~ e~rl in ~able 1:-SUBSTITUTE SHEEr l~ULE 26 W0951219~8 ? ~ 8 ~ 8 ~ "~
.~
o U o X C, ,~ ~, N r ~ C~
~r .
L L
", ; L' ~
CC CC 3 0 ~
0 5 Z Z 3: 0 U O Z
C
.
C C~
1:~ 2 ~ ~ '~ ~r ~ C ~, ~ C _ _ _ ~ ~ ~ 2 ~ 3 r T ~ ~ 5 = ~r .
C~
c c c c ~ .r c O .. ~
SUBSTITU~E SHEEr tRULE 26) WO9S/21958 2 1 8~ ~2 lo P~
E~r e~urples of dyes made see I~le 1.
r- 18 Pr~r~tirn of 1-smino-2-fll1nrnc-l~nhnnvl-4- (N-nh~n l) . ~
S 1-Ami~o-(N-phenyl~ _ 2-sulpho~ic iacid (2.5 parts~ was heated 1 pyridine (100 parts~ at reflux for 2 hours. The reaction mi~cture wa~ filtered a~d the pyrirqin~ removed on a rotary ev~ul IL~L to yield 2.3 parts of t_e pyrirlin:Lum salt.
The pyrir~irium salt (1 part~ vas heated at 75C for 4S
mi~utes in K~Cl (20 par~s~ . On cool~y the reaction mixture was poured illto ice/ivater fil~ered an~ the resultiDg solid was washed 5ev~al times with water. me sulrhonyl chloride was heated at 100C for 3 hours w~th L ' fluoride (3 parts~ in 1 4-di = (47 parts~/water (22 parts~
After coolily the reaction mixture was filtered and the solid obtained washed with wiqter to yield 1-ami~o-2-fll-rim~-lrh nyl-4-(N-phenyl~ ` nnn~ (0.2 p rts~ .
~ 1f' 19 i prPn=r=tinn of l-alTiLno-2-fllmmc llnhnnvl-4- ~N- (3-sul~honvlethvl sul~hc7rlic Ari 1~nh-~nvl i nnn~
1-Amino -4- (N- ( 3 - sulphonylethyl ~-1 rhnn; r acid) phenyl ~ amino--2-sulphonic acid (1.2 parts~ was heatel to reflux in -pyridine (814 parts~ _or 24hours. me pyridine was removed by rou~y evc~L~L L a~d the ~esulting solid washed with petroleum ether (b. pt.
60-80C~to give the dipyridinium salt which was dissolved in ~MF (972 parts~ and thionyl chloride (340 parts~ was ad~ed dropwise. me mixture was heated at 80C ~or 4-5 hours cooled poured into water alld filtered to ive the sulphonyl chloride ~iv-~iv=.
me sulphonyl chloride leLivcL~Lve (1.76 parts) was heated at 80C for 18 hours with fluoride (13.5 parts~ in 1 4-dioxan (468 parts)/water (555 parts~ . ~fter cooling the solvents were removed on a rotary ev~l~ .l . to yield a solid which was washed with watOE ~efore kei~ig dissolved in acetone and screened throu~h silica. me acetone was removed to yield 1-amino-2-f1-1nmq -1rhrnyl-4- (N- (3-sulphonylethy~ rhnnir acid)phenyl - i~ _ ril2Dm.
r 1 f 20 ii~n~l 21:
pr ni~r~tinn of l-amino-2-fllmrnqnlnhnnvl-4- (N- (4-flllnrnclllnhnnvl)nhl~nvl) and 1 -2-flllnm~lllnhn 4- (N- (2 4- 1i fllmmcnlnhnnvl)~henvl~ ~.
l-Amino-2-rhlnrn~-lrhnnyl-4- (N-phenyl) nnn~ (1 }) was added to a stirred mixture of rh1nrn~11rhnnir acid (35 parts) and thionyl c-hloride (8 parts~ a~d heated at 65C for 2.5 hours. After cooling to room t~ the reaction mixt~lre was po~2 ed ;ntn r 45 ice/water and filtered to yield a solid which was washed several times SUBSTITUTE SHEET (RULE 26) W09St'~1958 2 1 8 ~ ~ 5 ~ I ~1. . , wit_ water. Ihe solid was heated at 100C _or 2 hours with ~ ' fluoride (40 parts) in 1,4-diosn (480 parts~/water (440 parts~. On ccoling, th~ reaction mixture was filtered and the solid obtained washed with water to gil~e l-=o-2-fll~nrnnllrhn"yl-4-(N-(4-S fllmrnnllrhnnyl~phenyl~ a~d l-amino-2-fllmrnnllrhnn 4-(N-(2,4-~l;flllnrnnllrhnnyl~p~nyl~ = 534nm. The ~s may be ~PrPr-AtPr1 1' rAlly r 1P 22 pn~l 23 pr~nprAtinn of 1~5-dihv~ro7cv-2~6-~l;nlmrnn~lnhnnvl-4~8-Al111; nnnP and 1.5-dih~drwcv-2-flvnr~snl~hr,nVl-4,8-~ 6 rh1 1 ~
1,5-Di=o-3,7-~l;n-l~ ,ll",.. ,r", (2.7 parts~ was heated in pyri~;nP (10 parts~ at reflux for 2 hours. The solution was th~n filtered and thle pyridine removed on a rotary eVW~LCLLUL to yield the dipyridinium salt (2.5 parts).
~he pyri~linium salt (0.47 parts) was heated at 75C for 9 hours in PCC13 (107 parts). After addi~g toluene (235 parts) the reacticn mixture was heated at 120C for 3 hours. After cooling, the reaction mixture was filtered and the resultillg solid sulphonyl chloride was was_ed sevOEPl times with water. The sulphcnyl chloride was heated at 100C for 3 hours with, ' flucride (1.7 parts) in 1,4-di~ (59 parts) . After cooling, the reaction mixture was filtered a~d the solid obtained washed with water to give 1~5-dihydrcncy-2~6-~l;nllnrn 4,8--i; - nnnr and 1~s-dihydrcocy-2-flllnrnnllrhrnyl-4~a-diamin 6-rhl~ . Ihe product was a mixture of 22 a~d 23, with 23 ~eing th~ ma~or _ of the mixture.
~ lw 24:
p~nprwtirn of 1 ' ~ (N-(4-fll~nrnnllnhnnvl)~henv3~) ;II I.~IIIll _~lll;ll~ IIG
(3.3 parts), sodium acetate (5 parts), cupric acetate (0.5 parts~ and sulphanilyl fluoride (4 parts~
were stirred in o-~l;rhl,,.~.l~. . ~ (88 parts) at 1~0C for 30 hours. The solution was allcwed to cool and filtered, the solid was washed with 35 WatOE several times to give l-amino-4-(N- (4-flllnrnnllrhnnyl~phenyl) r 1~ 7sprPnRrRtinn of 1 ~ hvArn~-2- (4-40 fllmmnll l"" vl"l,_" "v)~"ll .. ";, A m~xutre o~ l-amino-4-hy~roxy-2-~ y_"l l", l,;, " _ (0.2g) was stirreA
aver~ight with flllnrnnllrhnn;r acid (10c~) and poured onto ice. The rr~rinitRt~i solid was rnll~rt~ by filtr~tinn ~nA washed with water and dried to gi~e l-amino-4-hy~r~Ly-2-phen~y ,."l 1, ~ (0.17g, 70'6) .
SUBSTITUTE SHEET tRULE 26~
Claims (4)
1. A process for colouring an aromatic polyester or fibre blend thereof which comprises applying to the aromatic polyester a compound of Formula (1):
Formula (1) wherein:
Ring A and Ring D are optionally substituted and at least one of Ring A or Ring D
carries at least one -SO2F group except for 2-[(9,10-dihydro-9,10-dioxo-1-anthracenyl)amino]-ethanesulphonylfluoride, 2-[(9,10-dihydro-9,10-dioxo-2-anthracenyl)amino]-ethanesulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,5-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-2-methoxy-9,10-dioxo-1,4-anthracenediyl)diimino) bisethanesulphonylfluoride, 2-[(4-(benzoylamino)-9,10-dihydro-9,10-dioxo-1-anthracenyl]amino]
ethanesulphonylfluoride, 2-[(9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl]amino]ethane sulphonylfluoride.
Formula (1) wherein:
Ring A and Ring D are optionally substituted and at least one of Ring A or Ring D
carries at least one -SO2F group except for 2-[(9,10-dihydro-9,10-dioxo-1-anthracenyl)amino]-ethanesulphonylfluoride, 2-[(9,10-dihydro-9,10-dioxo-2-anthracenyl)amino]-ethanesulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,5-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-2-methoxy-9,10-dioxo-1,4-anthracenediyl)diimino) bisethanesulphonylfluoride, 2-[(4-(benzoylamino)-9,10-dihydro-9,10-dioxo-1-anthracenyl]amino]
ethanesulphonylfluoride, 2-[(9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl]amino]ethane sulphonylfluoride.
2. A compound of Formula (1):
Formula (1) wherein:
Ring A and Ring D are optionally substituted and at least one of Ring A or Ring D
carries at least one -SO2F qroup except for 2-[(9,10-dihydro-9,10-dioxo-1-anthracenyl)amino]-ethanesulphonylfluoride, 2-[(9,10-dihydro-9,10-dioxo-2-anthracenyl)aminol-ethanesulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,5-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-2-methoxy-9,10-dioxo-1,4-anthracenediyl)diimino) bisethanesulphonylfluoride, 2-[(4-(benzoylamino)-9,10-dihydro-9,10-dioxo-1-anthracenyl]amino]
ethanesulphonylfluoride, 2-[(9,10-dihydro4-(methylamino)-9,10-dioxo-1-anthracenyl]amino]ethane sulphonylfluoride, 1-N-(4-methyl-3-fluorosulphonylphenyl)amino-4-N-methylaminoanthraquinone, 1-N-methylamino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-5-fluorosulphonylanthraquinone, 1-N((4-fluorosulphonyl)benzyl)amino-4-methylaminoanthraquinone, and 1-amino-4-N-phenylamino-2-fluorosulphonylanthraquinone.
Formula (1) wherein:
Ring A and Ring D are optionally substituted and at least one of Ring A or Ring D
carries at least one -SO2F qroup except for 2-[(9,10-dihydro-9,10-dioxo-1-anthracenyl)amino]-ethanesulphonylfluoride, 2-[(9,10-dihydro-9,10-dioxo-2-anthracenyl)aminol-ethanesulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,4-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-9,10-dioxo-1,5-anthracenediyl)diimino]bisethane sulphonylfluoride, 2,2'-[(9,10-dihydro-2-methoxy-9,10-dioxo-1,4-anthracenediyl)diimino) bisethanesulphonylfluoride, 2-[(4-(benzoylamino)-9,10-dihydro-9,10-dioxo-1-anthracenyl]amino]
ethanesulphonylfluoride, 2-[(9,10-dihydro4-(methylamino)-9,10-dioxo-1-anthracenyl]amino]ethane sulphonylfluoride, 1-N-(4-methyl-3-fluorosulphonylphenyl)amino-4-N-methylaminoanthraquinone, 1-N-methylamino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-5-fluorosulphonylanthraquinone, 1-N((4-fluorosulphonyl)benzyl)amino-4-methylaminoanthraquinone, and 1-amino-4-N-phenylamino-2-fluorosulphonylanthraquinone.
3. A compound of Formula (2):
Formula (2) in which:
R1 and R2 each independently is -H, or alkyl, alkylaryl, aryl or -COaryl optionally substituted by -SO2F, -OH, alkoxy or alkylOH, or -SO2aryl optionally substituted by -SO2F, -SO2alkylOSO3H or alkyl;
R3 is -H, -Cl, -Br, -SO2F or alkyl, alkylOCOaryl, aryl, cycloalkyl, heterocycloalkyl, alkoxy, aryloxy, alkylthio, arylthio, heteroarylthio or -SO2aryl each of which is optionally substituted by -OH, alkyl, alkoxy, -OCOOalkyl, , -SO2NHalkylalkoxy,-SO2F, -COOalkyl or -OCOaryl;
R4 is -H, -SO2F, -Cl, -Br, -CN or aryl or aryloxy each optionally substituted by -OH, -SO2F or-OCOOalkyl;
or R3 and R4 together with the carbon atoms to which they are attached form a 5-membered heterocyclic ring;
Z is-H, -OR1, SR1, -NR1R or-COaryl;
R5 and R8 each independently -H, -NO2, -OR1, -NR1R or-SO2F; and R6 and R7 each independently is -H, -SO2F or halo;
provided that when R1 is -H, R is not -C2H4SO2F and except for 1-N-(4-methyl-3-fluorosulphonylphenyl)amino-4-N-methylaminoanthraquinone, 1-N-methylamino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-5-fluorosulphonylanthraquinone, 1-N((4-fluorosulphonyl)benzyl)amino-4-methylaminoanthraquinone, and 1-amino-4-N-phenylamino-2-fluorosulphonylanthraquinone.
Formula (2) in which:
R1 and R2 each independently is -H, or alkyl, alkylaryl, aryl or -COaryl optionally substituted by -SO2F, -OH, alkoxy or alkylOH, or -SO2aryl optionally substituted by -SO2F, -SO2alkylOSO3H or alkyl;
R3 is -H, -Cl, -Br, -SO2F or alkyl, alkylOCOaryl, aryl, cycloalkyl, heterocycloalkyl, alkoxy, aryloxy, alkylthio, arylthio, heteroarylthio or -SO2aryl each of which is optionally substituted by -OH, alkyl, alkoxy, -OCOOalkyl, , -SO2NHalkylalkoxy,-SO2F, -COOalkyl or -OCOaryl;
R4 is -H, -SO2F, -Cl, -Br, -CN or aryl or aryloxy each optionally substituted by -OH, -SO2F or-OCOOalkyl;
or R3 and R4 together with the carbon atoms to which they are attached form a 5-membered heterocyclic ring;
Z is-H, -OR1, SR1, -NR1R or-COaryl;
R5 and R8 each independently -H, -NO2, -OR1, -NR1R or-SO2F; and R6 and R7 each independently is -H, -SO2F or halo;
provided that when R1 is -H, R is not -C2H4SO2F and except for 1-N-(4-methyl-3-fluorosulphonylphenyl)amino-4-N-methylaminoanthraquinone, 1-N-methylamino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-4-N-benzylamino-2-fluorosulphonylanthraquinone, 1-amino-5-fluorosulphonylanthraquinone, 1-N((4-fluorosulphonyl)benzyl)amino-4-methylaminoanthraquinone, and 1-amino-4-N-phenylamino-2-fluorosulphonylanthraquinone.
4. A process for the mass coloration of plastics which comprises incorporating into a plastics material a compound or mixture thereof which is free from water solubilising groups, of Formula (1) wherein Ring A and Ring D are as hereinbefore defined and at least one of Rings A or D carries directly at least one -SO2F group or carries a substituent to which at least one -SO2F group is attached.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9402607A GB9402607D0 (en) | 1994-02-10 | 1994-02-10 | Process |
| GB9402607.7 | 1994-02-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2180852A1 true CA2180852A1 (en) | 1995-08-17 |
Family
ID=10750203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002180852A Abandoned CA2180852A1 (en) | 1994-02-10 | 1995-01-23 | Anthraquinone dyes containing a fluorosulphonyl group and use thereof |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US5759211A (en) |
| EP (1) | EP0743994B1 (en) |
| JP (1) | JP3893149B2 (en) |
| KR (1) | KR970701284A (en) |
| AU (1) | AU1540095A (en) |
| CA (1) | CA2180852A1 (en) |
| CO (1) | CO4370117A1 (en) |
| DE (1) | DE69526430T2 (en) |
| ES (1) | ES2174924T3 (en) |
| GB (1) | GB9402607D0 (en) |
| IN (1) | IN190255B (en) |
| TW (1) | TW306942B (en) |
| WO (1) | WO1995021958A1 (en) |
| ZA (1) | ZA95793B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6140517A (en) * | 1996-09-03 | 2000-10-31 | Eastman Chemical Company | Anthraquinone polysulfonamide colorants |
| GB0217487D0 (en) * | 2002-07-29 | 2002-09-04 | Dystar Textilfarben Gmbh & Co | Non-azo disperse dye mixtures |
| EP1533105A1 (en) * | 2003-10-15 | 2005-05-25 | Orient Chemical Industries, Ltd. | Laser-transmissible colored resin composition and method for laser welding |
| EP1820826A1 (en) * | 2006-02-09 | 2007-08-22 | DyStar Textilfarben GmbH & Co. Deutschland KG | Dyestuffs and Hair Dye Compositions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2576037A (en) * | 1947-08-25 | 1951-11-20 | American Cyanamid Co | Sulfonyl fluorides of amino azo dyestuffs |
| US3952029A (en) * | 1975-01-13 | 1976-04-20 | Eastman Kodak Company | 2-(Fluorosulfonyl)ethylamino anthraquinones |
| JPS6024865B2 (en) * | 1977-09-27 | 1985-06-14 | 三菱化学株式会社 | Thermal transfer printing method for cellulose-containing materials |
-
1994
- 1994-02-10 GB GB9402607A patent/GB9402607D0/en active Pending
-
1995
- 1995-01-23 TW TW084100574A patent/TW306942B/zh not_active IP Right Cessation
- 1995-01-23 EP EP95907057A patent/EP0743994B1/en not_active Expired - Lifetime
- 1995-01-23 US US08/693,195 patent/US5759211A/en not_active Expired - Lifetime
- 1995-01-23 AU AU15400/95A patent/AU1540095A/en not_active Abandoned
- 1995-01-23 JP JP52102995A patent/JP3893149B2/en not_active Expired - Fee Related
- 1995-01-23 WO PCT/GB1995/000097 patent/WO1995021958A1/en active IP Right Grant
- 1995-01-23 DE DE69526430T patent/DE69526430T2/en not_active Expired - Lifetime
- 1995-01-23 ES ES95907057T patent/ES2174924T3/en not_active Expired - Lifetime
- 1995-01-23 KR KR1019960704359A patent/KR970701284A/en not_active Application Discontinuation
- 1995-01-23 CA CA002180852A patent/CA2180852A1/en not_active Abandoned
- 1995-01-23 IN IN88DE1995 patent/IN190255B/en unknown
- 1995-02-01 ZA ZA95793A patent/ZA95793B/en unknown
- 1995-02-09 CO CO95004918A patent/CO4370117A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW306942B (en) | 1997-06-01 |
| JPH09509200A (en) | 1997-09-16 |
| ES2174924T3 (en) | 2002-11-16 |
| WO1995021958A1 (en) | 1995-08-17 |
| JP3893149B2 (en) | 2007-03-14 |
| CO4370117A1 (en) | 1996-10-07 |
| DE69526430D1 (en) | 2002-05-23 |
| IN190255B (en) | 2003-07-05 |
| US5759211A (en) | 1998-06-02 |
| EP0743994A1 (en) | 1996-11-27 |
| ZA95793B (en) | 1996-08-12 |
| GB9402607D0 (en) | 1994-04-06 |
| AU1540095A (en) | 1995-08-29 |
| DE69526430T2 (en) | 2002-12-12 |
| EP0743994B1 (en) | 2002-04-17 |
| KR970701284A (en) | 1997-03-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |